Copper-containing polyazo dye



United States Patent Ofiice 3,285,904 Patented Nov. 15, 1966 This invention is a continuationdn-part application to copending application Ser. No. 101,375, filed on April 7, 1961, and now abandoned, and it relates to a new and valuable copper-containing polyazo dye.

The new dye of the present invention is produced by coupling in any desired order (a) one mole of the diazo compound of an aminoazo dye, formed by coupling a diazomonoazo or diazodisazo compound containing in ortho-position to the diazo group a snbstituent permitting the formation of copper complex compounds, with 1- amino-S-hydroxyn-aphthalene-3,6-disulfonic acid in the 7- position thereof, and (b) one mole of a diazo or diazomonoazo compound, which contains in ortho-position to the diazo group a substituent permitting the formation of copper complex compounds with one mole of 1,3-dihydroxy-4-chlorobenzene, and treating the resulting polyazo dye which contains three sulfonic acid groups, in substance with a copper-yielding agent.

Alternatively, the diazo compound (a) or the diazo compound (b) can be coupled first with 1,3-dihydroxy-4- chlorobenzene, the intermediate thus formed treated with a copper-yielding, agent, and the copper complex compound coupled with the diazo compound (b) or the diazo compound (a) to give the poly-azo dye which is finally treated in substance with a copper-yielding agent. The new dye has the formula in addition to the presence of an alkaline agent such as ammonia or sodium carbonate the addition of a diazo stabilizer such as naphthalene-Z-sulfonic acid and in certain cases an agent for promoting the coupling reaction,

5 for example pyridine.

The copper complex compound can be prepared in the conventional manner, most advantageously by heating an aqueous paste or solution of the dye containing a copper-yielding agent and an alkaline salt oi a low-molecular aliphatic carboxylic acid.

In the example the parts and percentages are by weight and the temperatures in degrees centigrade.

Example The disazo dyestutf, prepared in per se conventional manner from 24.4 parts of tetrazotized 4,4'-diamino-3.3- dimethoxy-1,1'-diphenyl, 13.8 parts of l-hydroxybenzene- 2-carboxylic acid and 31.9 parts of I-amino-S-hydroxynaphthalene-3,6-disulfonic acid, is dissolved in 2000 parts of water after which 6.9 parts of sodium nitrite are added,

of l-methoxy-2-aminobenzene-4-sulfonic acid. The soobtained olive-dyed tetrakisazo dyestuff is filtered ofi" and is purified by reprccipitation from hot water.

For conversion of the said tetraki-sazo dyestuif into the copper complex compound, the former is dissolved in 3000 5 parts of water, after which parts of sodium acetate The preferred mode of production consists in coupling the disazo dye prepared from tetrazotized 4,4'-diamino-3.3'dimethoxy-2-carboxylic acid and 1-am-ino-8- hydroxy-3.6-disulfonic acid with 1,3-dihydroxy-4-chlorobenzene to give a trisazo dye which is coupled with the diazo compound of l-methoxy-2-aminobenzene-4-sulfonic HOOC | I I I and 50 parts of crystalline copper sulfate are added to the solution which is then heated in an enameled pressure vessel for 4 to 6 hours at -120", until the color has changed to a dark brown. The dyestufi is then salted 50 out with sodium chloride, filtered and dried.

The dye has the formula and is obtained as a dark powder which dissolves in water With a dark brown and in concentrated sulfuric acid with a violet-brown coloration. It dyes cotton, viscose filament and staple fiber and other regenerated cellulosic fibers in dark brown shades. The dyeings on these fibers have excellent perspiration fastness, especially when a creaseresistant resin finish is applied, and good fastness to light, washing, water, sea water and milling. The dyeings do 0 not undergo a change of shade when submitted to these wet treatments or exposed to light.

An unexpected property shown by the dye is its stability in aqueous solution over a period of several days, an imthoroughly rinsed and dried. It is dyed in a black-brown portant point in dyeing where stock solutions are often shade. prepared in advance for use as required. The fastness properties of the dyeing can be further en- The dye can be applied to the cotton or viscose rayon hanced by a treatment with a copper-containing polycomponent of blends with triacet'ate fiber; it reserves the 5 alkylene-polyamine. To this end, 100 parts of dyed and triacetate component White. It can be shown that the dried cotton are introduced at 30 into a bath consisting same excellent triacetate reserve is obtained when an aqueof 3000 parts of water and 2 parts of a copper-containing ous stock solution of the dye is applied after several polyalkyle -p The bath is mated to days storage, which is surprising since this is not the the dyed cotton is kept therein for 30 minutes. Therecase with similar other known dyes containing 1,3-dihyupon the dyed and treated cotton is rinsed and dried. Its droxybenzene as coupling component. These latter dyes shade remains unchanged. stain the triaceta-te component of blends with cellulosie Cotton-triacetate and viscose rayon-triacetate blend fibers and thus are unsuitable for dyeing these materials. fabrics can be dyed on similar lines with a white reserve I of the triacetate component.

Having thus disclosed theinvention What I claim is: 100 parts of cotton are entered at room temperature The copper complex compound of the poly-azo dye cor- (abOut -30") into a solution of 0.6 part of the dyestuff responding to the formula Dyeing example Hoot H 00 O- Cu0 N=N N'=N HO3S SO;H S0311 prepared according to the example and 2 parts of tr-isodi- References Cited by the Examiner um phosphate (or sodium metaphosphate or trisodium polyphosphate) in 3000 parts of water, with the addition UNITED STATES PATENTS of 10 parts of Glaubers salt. The dyebath is heated to 2,870,135 1/1959 Semi 260-145 boiling temperature in the course of minutes. During 30 such heating, an additional 10 parts of Glaubers salt are OTHER REFERENCES added. Dyeing of the cotton is carried out at boiling tem- Colour Index, vol. 3, 2nd ed., page 3598 (1956).

perature for 15 minutes. At the end of this time, 20 more parts of Glaubers salt are added; after which the dyeing 3 CHARLES B. PARKER, Primary Examiner. is completed in the course of 15-20 minutes in the cooling bath. The cotton is withdrawn from the bath, is FLOYD HIGEL Asslsmnt Exammer' 

